GB2117387A - Silicone-containing contact lens material and contact lenses made thereof - Google Patents

Silicone-containing contact lens material and contact lenses made thereof Download PDF

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Publication number
GB2117387A
GB2117387A GB08304358A GB8304358A GB2117387A GB 2117387 A GB2117387 A GB 2117387A GB 08304358 A GB08304358 A GB 08304358A GB 8304358 A GB8304358 A GB 8304358A GB 2117387 A GB2117387 A GB 2117387A
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contact lens
clme
siloxane
accordance
lens material
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GB08304358A
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GB2117387B (en
GB8304358D0 (en
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Edward James Ellis
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Polymer Technology Corp
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Polymer Technology Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Description

.DTD:
1 GB 2 117 387 A 1 .DTD:
SPECIFICATION .DTD:
Silicone-containing contact lens material and contact lenses made thereof Soft contact lenses can be divided into two basic types, water absorptive and non-water absorptive. Water absorptive lenses commonly are referred to as hydrogel lenses and are generally prepared from 2-hydroxyethyl methacrylate (HEMA) or copolymers with HEMA as the major 5 component. High water content lenses have also been produced from vinylpyrrolidone. Non-water absorptive soft contact lenses are produced from silicone rubber or like materials. Such soft contact lenses can have one or more of the following disadvantages: poor durability, less visual acuity than hard lenses, poor oxygen permeability, and/or ease of bacterial contamination.
.DTD:
Hard contact lensesproduced from polymethyl methacrylate (PMMA) have been known in the art 10 for many years and offer the advantages of optical clarity, dimensional stability and durability. Although PMMA has been the standard of the hard contact lens industry, it has at least two drawbacks. Because PMMA is marginally hydrophilic a lens wearer may experience discomfort as a result of a foreign body -. reaction. Secondly, oxygen gas transport through PMMA contact lenses is extremely low which dictates that the lenses cannot be worn continuously for an extended period of time. Since the cornea receives 15 its oxygen directly from the atmosphere the PMMA lens wearer often experiences corneal swelling and irritation due to prolonged oxygen deprivation.
.DTD:
Within the past ten years commercial cellulose acetate butyrate (CAB) has been utilized in an attempt to provide a hard contact lens that will transport oxygen. Although CAB exhibits modest oxygen permeability it lacks other essential qualities necessary for a contact lens material. The scratch or mar 20 resistance of CAB contact lenses is poor which may be a reflection of the relative softness of CAB when compared to PMMA. Additionally, CAB lenses are often dimensionally unstable.
.DTD:
More recently, siloxane containing copolymers have been introduced as oxygen gas permeable hard contact lens materials. These polymeric composltions are generally prepared by copolymerizing 24 methyl methacrylate with a siloxanyl alkyl ester of methacrylic acid. Contact lenses conta|n|ng 25 substantial amounts of organosiloxane groups tend to be hydrophobic. Attempts to impart hydrophilic properties to such systems include the incorporation of a wetting agent and treatment of the lens surfaces. Incorporation of a wetting agent can improve the wettability of the lens but may also render the lens translucent when used in excessive amounts. Contact lenses containing such wetting agents can be tolerated by the wearer but tend to accumulate proteinaceous matter 30 from the tear fluid. This results in decreased transparency of the lens and wearer discomfort.
.DTD:
Surface treatment of the lens affords a wettable surface but can lack permanence. Any scratches or adjustments made on such lenses exposes the hydrophobic bulk material. Repeated surface treatment is then necessary which can be inconvenient.
.DTD:
The contact lens field has long known the advantages of silicone polymers for use in contact 35 lenses. Poly(dimethylsiloxane) polymers are transparent and highly permeable to oxygen, although Use of these polymers in contact lenses can present difficulties in the fabrication and finishing of lenses because of the rubbery nature of the polymers. Contact lenses produced from poly(dimethylsiloxane) are often inherently hydrophobic and often must be surface treated to render the surfaces wettable by tears. - It's known that the use of a methacrylate monomer containing a silicone moiety can be 40 copolymerized with the standard monomer utilized in conventional hard contact lenses, i.e., methyl methacrylate, to obtain a copolymer of varying hardness values depending upon the ratio of hard and soft monomers employed. Thus, some attempts have been made in the art to produce hard oxygen- permeable contact lenses. For example, U.S. Patent No. 3,808,178 discloses a copolymer of methyl methacrylate with a siloxanyl alkyl ester of methacrylic acid. The use of special wetting agents and 45 cross-linking agents are also taught in U.S. Patent No. 3,808,178.
.DTD:
In U.S. Patent No. 4,152,508 the use of an itaconate ester copolymerized with a siloxanyl alkyl ester of methacrylic acid is disclosed. The siloxanyl alkyl ester provides for high permeability and the itaconate ester gives increased rigidity, hardness and some degree of wettability. In addition, specific cross-linking agents and hydrophilic monomers are incorporated which provide dimensional stability 50 and wettability to contact lenses generated therefrom.
.DTD:
The composftions disclosed in U.S. Patent Nos. 4j16,303 and 4,242,483 are branched siloxanyl alkyl esters of methacrylic acid essenti.ally as suggested by the prior patents.
.DTD:
U.S. Patent Nos. 4,153,641 and 4,189,546 teach the use of monomeric polysiloxanes end capped with activated, unsaturated groups. By varying the type and amount of comonomer as well as the 55 moiety both hard and soft polymeric compositions are said to be possible., o-Bis- (4methacryloxybutyl) polydimethylsiloxane is disclosed in which the poly(organosiloxane) moiety varies from about 0 to 800 units in length. For a hard contact lens the poly(organosiloxane) moiety should be of a rather short length, perhaps 0 to 10 units long, to avoid incompatibility in the final composition due to phase separation. Therefore, when comparing the monomeric polysiloxanes disclosed in both U.S. 60 Patent Nos. 4,153,641 and 4,189,546 with siloxanyl alkyl esters of methacrylic acid disclosed in U.S.
Patent Nos. 3,808,178 and 4,152,508, on the basis of utility in gas permeable hard contact lens compositions, similarities are noted. Whereas the siloxanyl alkyl esters of methacrylic acid disclosed in 3,808,178 and 4,152,508 are monomers, that is, contain one polymerizable unsaturated group, the 2 GB 2 117 387 A 2 monomeric polysiloxanes disclosed in 4,153,641 and 4,189,546 contain two such polymerizable unsaturated groups.
.DTD:
U.S. Patent 4,259,467 discloses polysiloxanes containing hydrophilic side chains. These materials are generally rubbery and absorb water which makes them particularly suitable for soft contact lenses.
.DTD:
The patent does teach the advantages of an inherently hydrophilic polysiloxane. Patent 4,261,875 6 discloses polysiloxanes which contain hydroxyalkyl side chains which import hydrophilicity to the ! polymer. These polysiloxanes are copolymerized with other hydrophilic monomers to produce water absorbing compositions which are useful in soft contact lenses. Many of these prior art polysiloxanes are water absorbing to a degree greater than 2%. This can effect dimensional stability of contact lenses made with these materials. 10 It is an object of this invention to provide novel substituted alkyl or aryl siloxanes containing one or more unsaturated polymerizable groups which are particularly useful when polymerized alone or with modifying comonomers for optical contact lenses.
.DTD:
Still another object of this invention is to provide high quality optical contact lenses formed of substituted alkyl or aryl polysiloxanes containing one or more unsaturated or polymerizable.groups and 15 having high polarity with under about 2% water absorption and which tend to avoid the tendency to accumulate proteinaceous matter in use.
.DTD:
Still another object of this invention is to provide organosilanes in accordance with the preceding objects for use as contact lenses which are easily wettable.
.DTD:
According to the invention a substituted alkyl or aryl siloxane contains one or more unsaturated 20 polymerizable groups and has the following formula:
.DTD:
0 I X- K - $c-- R-X I X I j / o.
f I X r"t,, X I g I S-R-x 0 ! X - R - $c- R-X R i X = wherein:
.DTD:
X is an unsaturated polymerizable methacrylate or acrylate group or hydrogen or "Z group; R can be an alkylene or cycloalkylene group having from 1 to about 10 carbon atoms, or an 25 arylene group. Each "R group may be the same or different. The arylene group is preferably phenylene.
.DTD:
a is an integer from 0 to about 10 where each "a" may be the same or different.
.DTD:
n is an integer from 0 to about 10.
.DTD:
Z groups are acetoxy, carbomethoxy, glycidoxy, glyceryl, and carboxy. Acetoxy and carbomethoxy groups are preferred. At least one "X" is a "Z" group. 30 The above siloxane can be polymerized by free radical polymerization as a homopolymer or with other monomers and materials to form contact lens materials useful for forming rods, buttons and machinable or otherwise formable into final contact lens products.
.DTD:
Particularly novel and useful siloxanes according to this invention are 1,3-bis(?-meth acryloxypropyl- 1,1,3,3-tetra(3acetoxypropyldimethylsiloxy)disiloxa ne 35 p-methacryloxypropyl-tris(4-acetoxyphenyldimethylsiloxy)silane 3 GB 2 117 387 A 3 -methacryloxypropyl-tris(2-carboxyethyldimethylsiloxy)silane F-methacryloxypropyl-tris(2-acetoxyethyldimethylsiloxy)silane 1 -F-methacryloxymethyl-3-(3-acetoxypropyl)- 1,1,3,3- tetramethyldisiloxane -methacryloxypropyl-bis(trimethylsiloxy)-(3acetoxypropyldimethylsiloxy)silane -methacryxyprpy-bis(trimethysixy)-(3-carbmethxyprpydimethysixy)siane 5 -methacryloxypropyl-bis(trimethylsiloxy)-(3hydroxypropyldimethylsiloxy)silane -methacryloxypropyl-bis(trimethylsiloxy)-(3carboxypropyldimethylsiloxy)silane -methacryloxypropyl-bis(3-acetoxypropyldimethylsiloxy)-(trimethylsiloxy)-, silane ]-methacryxyprpy-bis(3-carbmethxyprpydimethysiixy)-(trimethysixy)siane F-methacryloxypropyl-bis(3-hydroxypropyldimethylsiloxy)(trimethylsiloxy)silane 10 F-methacryloxypropyl-bis(3-carboxypropyldimethylsiloxy)(trimethylsiloxy)silane F-methacryloxypropyl-tris(3-acetoxypropyldimethylsiloxy)silane F-methacryloxypropyl-tris(3-carbomethoxypropyldimethylsiloxy)silane y-methacryloxypropyl-tris(3-hydroxypropyldimethylsiloxy)silane T-methacryxyprpy-bis(pentamethydisxany)-(3-acetxyprpydimethysixy)siane 15 -methacryioxypropyl-bis(pentamethyldisiloxa nyl)-(3carbomethoxypropyldimethylsiloxy)silane T-methacryxyprpy-bis(pentamethydisixany)-(3-hydrxyprpydimethysixy)siane }-methacryloxypropyl.-bis(penta methyldisiloxanyl)-(3carboxypropyldimethylsiloxy)silane 1 -(F-methacryloxypropyl)-3-(3-acetoxypropyl)tetra(trimethylsiloxy)disiloxane 1-(-methacryxyprpy)-3-(3-carbmethxyprpy)-tetra(trimethysixy)disixane 20 1 -(T,-methacryloxypropyl)-3-(3-hydroxypropyl)tetra(trimethylsiloxy)disiloxane 1 -(y-methacryloxypropyl)-3-(3-carboxypropyl)tetra(trimethylsiloxy)disiloxane It is a feature of this invention that contact lenses formed from the siloxanes of this invention have a substantial content of organosiloxane to provide sufficient oxygen transport to the cornea. Good 25 oxygen permeability in accordance with the materials of this invention includes oxygen permeability in the range of from 25 to 300 cm3 mm/cm2sec cm Hg x 10-l for all contact lens materials.
.DTD:
In addition to high oxygen permeability, contact lenses and materials of this invention can be easily fabricated and finished, are dimensionally stable, inherently wettable, have high light transmission, are durable, biocompatible, non-hydrating, chemically stable and highly resistant to 30 proteinaceous accumulation as well as being scratch resistant. The contact lenses can be worn safely and comfortably for extended periods of time while providing the wearer with good vision.
.DTD:
The contact lenses formed from organosiloxanes in accordance with this invention can be of the known types. Thus hard or soft contact lenses can be formed using conventional machining, casting or molding techniques to form contact lenses from blanks, rods and batches of materials made in 35 accordance with conventional practice.
.DTD:
The organosiloxanes of this invention can be homopolymerized or copolymerized with each other. Other materials can be added to the contact lens materials as copo!ymers and include hardening agents. hydrophilic wetting agents and other additives such as tinting agents and the like.
.DTD:
It is preferred that the polyorganosiloxanes formed into contact lens materials and subsequent 40 40 contact lenses in accordance with this invention be inherently hydrophilic in nature. This provides uniform hydrophilic surfaces on contact lenses formed. Such contact lenses then exhibit less tendency to accumulate proteinaceous matter and provide the wearer with long- lasting comfort and visual acuity.
.DTD:
The water absorption of such lenses is preferably at or under 2% making it substantially non-water absorbent although hydrophilic thereby aiding and allowing great dimensional stability. 45 The materials are inherently more polar in nature than those presently utilized in contact lenses.
.DTD:
The added polarity aids in the hydrophilic nature of the lenses and also reduces the tendency for accumulation of mucoproteins.
.DTD:
The preferred alkyl or aryl siloxanes containing one or more unsaturated polymerizable groups in accordance with the present invention have the following formula: 50 4 GB 2 117 387 A 4 0 I y,, - I - S.-.-X i I X- K SL-?-X I 0 I %- K - So.- R-X I g I - lg-S- R-;,, I 0 I I S--x ! o 0 I g- So- "-X R X J wherein:
.DTD:
X is an unsaturated polymerizable methacrylate or acrylate group or hydrogen or "Z group; R can be an alkylene or cycloalkylene group having from 1 to about 10 carbon atoms, or an arylene group. Each "R group may be the same or different. The arylene group is preferably phenylene. a is an integer from 0 to about 10 where each "a'" may be the same or different. n is an integer from 0 to about 10.
.DTD:
Z groups are acetoxy, carbomethoxy, glycidoxy, glyceryl, and carboxy. Acetoxy and carbomethoxy groups are preferred. At least one "X" is a "'Z" group.
.DTD:
Preferably X is a Z group which is in turn an acetoxy or carbomethoxy group. The higher the acetoxy or carbomethoxy content, the higher the tendency to obtain softer more wettable materials.
.DTD:
Particularly useful materials for forming into contact lenses in accordance with this invention are the following:
.DTD:
= GB 2 117 387 A 5 C H= CH5- y-methacryloxypropyl-bis(trimethylsiloxy)-(3acetoxypropyldimethylsiloxy)silane CH3 i CIIZ= C i C-O i 0 | CH2, I CHúI 0 CH3 CH2" CH3 el " I -- t O CH3"-C O-CHCHú-CH-.'--o-S. O-S.;; -CHz..CH2_CH2_O_C._C.H3 CH3 0 CH3 i CH3- $L - C H3 ! CH5 y-methacryloxypropyl-bis(3-acetoxypropyldimethylsiloxyl(trimethglsiloxylsilane oo o p /,n (D 0 ! 1 0 I ! J ! j I 0 I ..J - -c..) I I I ! o ! ! -o - -,-.- - o,-.- <o I cO t3 (D r- A o E "o >.
.DTD:
o Q.
X o ? o0 _L >.
.DTD:
o o.
>.
.DTD:
x o E c -/.- Q) 0 SE".. ZZ" 0 -.-,0 I tl o J (D -.-o I o I O g ---0-o.-0-- 7 GB 2 117 387 A 7 y-methacryloxypropyl-bis(penta methyldisiloxanyl)-(3- acetoxypropyldimethylsiloxy)silane CH 0 0 CH3 1,3-bis(y-methacryloxypropyl)-I,1,3,3 tetra (3acetoxypropyldimethylsiloxy)disiloxane 8 GB 2 117 387 A 8 1 -(F-methacryloxypropyl)-3-(3-acetoxypropyl)tetra(trimethylsiloxy)disiloxane c ! Cl-2 = C! C=O I o I fHz H I 0 CH5 i CH5- 5L - c 3 o I C=O I CH,.5 9 GB 2 117 387 A 9 y-methacryloxypropyl-tris(4-acetoxyphenyldimethylsiloxy)silane y-methacryloxypropyl-tris(3-hydroxypropyldimethylsiloxy)silane 5. y-methacryloxypropyl-tris(2-carboxyethyldimethylsiloxy)silane 5 GB 2 117 387 A 10 o CHs d! C H3 -O-C -C:'H:2,-C H2 -5 ',. --0 -- I C it3 CH6- CH3 C I C=O 0 I | c2 CH2", ell3, 0 SL 0--SL.-.CH2,_CH2,t i, -C- O-C. H5 0 CH3 I 5i.- OH5 | C H.
cH2 C=O I 0 I CH5 y-methacryloxypropyl-tris(2-acetoxyethyldimethylsiloxy)silane CH3 I C H2.= C I C=O I 0 I CH CHS-IL-CH 0 I CH-sL- CH..5 i cu 0 | C"O I CH3 1 -y-methacryloxymethyl-3-(3-acetoxypropyl)- 1,1,3,3-tetra methylsiloxa ne Y-methacryxyprpy-bis(trimethysixy)-(3-carbmethxyprpydimethysixy)siane ymethacryloxypropyl-bis(trimethylsiloxy)-(3hydroxypropyldimethylsiloxy)silane y-methacryloxypropylbis(trimethylsiloxy)-(3-carboxypropyldimethylsiloxy)silane Ymethacryxyprpy-bis(3-carbmethxyprpydimethysixy)-(trimethysixy)siane ymethacryloxypropyl-bis(3hydroxypropyldimethylsiloxy)_(trimethylsiloxy)silane y-methacryloxypropyl-bis(3carboxypropyldimethylsiloxy)_(trimethylsiloxy)silane 11 GB 2 117 387 A 11 F-methacryloxypropyl-tris(3-carbomethoxypropyldimethylsiloxy)silane }-methacryxyprpy-bis(pentamethydisixany)-(3carbmethxyprpydimethysixy)siane P-methacryxyprpy-bis(pentamethydisixany)-(3-hydrxypropydimethysixy)siane }-methacryxyprpy-bis(pentamethydisixany)-(3-carbxyprpydimethysixy)siane 1 -(y-methacryxyprpy)-3-(3-carbmethxyprpy)-tetra(trimethysixy)disixane5 1 -(]}-methacryloxypropyl)-3-(3-hydroxypropyl)tetra(trimethylsiloxy)disiloxane 1 -(v-methacryloxypropyl)-3-(3-carboxypropyl)tetra(trimethylsiloxy)disiloxane It is understood that the examples given above should not limit the invention to substituted alkyl siloxanes since substituted phenyl groups, cyclohexyl and other groups are useful in this invention either alone or in combinations. Also, it is understood that each "X" group shown in the general structure may 10 be the same or different.
.DTD:
Preferably "Î", the unsaturated polymerizable groups, is chosen from among:
.DTD:
methacryloxy acryloxy Preferably "R", when a divalent alkyl group, is chosen from among: methylene ethylene propylene butylene cyclohexylene When "R" is aryl in nature the entire "RmX'' unit can be chosen from among:
.DTD:
substituted phenyl groups substituted benzyl groups substituted phenethyl groups substituted tolyl groups substituted xylyl groups The novel siloxane monomers employed in this invention are prepared utilizing techniques widely known in the art.
.DTD:
The comonomers used to modify the preferred siloxane materials of this invention when used, are those which are capable of undergoing free radical polymerization and enhance a desirable property such as machinability, durability, biocompatibility and hardness.
.DTD:
The term "hardening agent" as used in this application is meant to include comonomers which vary the hardness of copolymers formed with the siloxanes of this invention. Thus certain hardening agents can in fact cause a copolymeric material of this invention to be harder or softer than the siloxane if homopolymerized.
.DTD:
The derivatives of acrylic, methacrylic and itaconic acid such as esters of a C1--C2o monohydric or polyhydric alkanol or phenol and an acid selected from the class consisting essentially of acrylic and methacrylic acid, itaconate mono or diester or other known derivatives can be used as comonomers to act as hardening agents. Such hardening agents include:
.DTD:
methyl acrylate methyl methacrylate mono or di methyl itaconate ethyl acrylate ethyl methacrylate mono or di ethyl itaconate propyl acrylate propyl methacrylate mono or di propyl itaconate n-butyl acrylate n-butyl methacrylate mono or di n-butyl itaconate isopropyl acrylate isopropyl methacryate mono or di isopropyl itaconate hexyl acrylate hexyl methacrylate mono or di hexyl itaconate hepyl acrylate hepyl methacrylate mono or di heptyl itaconate cyclohexyl acrylate 12 GB 2 117 387 A 12 cyclohexyl methacrylate mono or di cyclohexyl itaconate 2-ethylhexyl acrylate 2-ethylhexyl methacrylate mono or di 2-ethylhexyl itaconate ethoxyethyl acrylate ethoxyethyl methacrylate mono or di ethoxyethyl itaconate butoxyethyl acrylate butoxyethyl methacrylate mono or di butoxyethyl itaconate 2-hydroxy ethyl acrylate 2-hydroxy ethyl methacrylate mono or di 2-hydroxy ethyl itaconate 2 or 3-hydroxypropyl acrylate 2 or 3-hydroxypropyl methacrylate mono or di 2 or 3-hydroxypropyl itaconate 3-methoxy-2-hydroxypropyl acrylate 3-methoxy-2-hydroxypropyl methacrylate mono or di 3-methoxy-2-hydroxypropyl itaconate tetrahydrofurfuryl acrylate tetrahydrofurfuryl methacrylate mono or di tetrahydrofurfuryl itaconate aryl acrylate aryl methacrylate 25 mono or di aryl itaconate allyl acrylate allyl methacrylate mono or di allyl itaconate glycidoxy acrylate 30 glycidoxy methacrylate mono or di glycidoxy itaconate Other comonomers may include hydrophilic wetting agents, N-vinylcarbazole, N- vinylpyrrolidone, hydroxy naphthyl methacrylate, styryls, such as styrene, methylstyrene, methoxy stryene and acetoxy styrene and allylic monomers, such as diallyl diglycol carbonate, diallyl phthalate, diallyl carbonate and 35 triallyl cyanurate.
.DTD:
The wettability of the compositions disclosed in this invention may be enhanced by the inclusion of hydrophilic agents such as neutral monomers, hydrophilic cationic monomers and hydrophilic anionic monomers and mixtures of these referred to as among the hydrophilic wetting agents herein. The classes of these compounds are hydrophilic acrylates and methacrylates, acrylamides, methacrylamides 40 and vinyllactams.
.DTD:
Representative hydrophilic neutral monomers include:
.DTD:
N-vinylpyrrolidone acrylamide methacrylamide 2-hydroxyethyl acrylate or methacrylate 2 or 3-hydroxyl propyl acrylate or methacrylate glyceryl acrylate or methacrylate glycidyl acrylate or methacrylate 3-methoxy-2-hydroxy propyl acrylate or methacrylate mono esters of acrylic and methacrylic acid with polyethers of the general formula:
.DTD:
Wherein "n" is a number from 1 to about 4 and "x" is a number from 2 to about 10.
.DTD:
The cationic monomers either can be initially in their charged form or are subsequently converted to their charged form after formation of the contact lens. The classes of these compounds are derived from basic or cationic acrylates, methacrylates, acrylamides, methacrylamides, vinylpyridines, vinylimidazoles, and diallyldialkylammonium polymerizable groups. Such monomers are represented by:
.DTD:
=q 13 GB 2 117 387 A 13 N,N-dimethylaminoethyl acrylate and methacrylate 2-methyacryloyloxyethyltrimethylammonium chloride and methylsulfate 2-, 4-, and 2-methyl-5-vinylpyridine 2-, 4-, and 2-methyl-5-vinylpyridinium chloride and methylsulfate N-(3-methacrylamidopropyl)-N,N-dimethylamine N-(3-methacrylamidopropyl)-N,N,N-trimethylammoniu m chloride N-(3-methacryloyloxy-2-hydroxylpropyl)-N,N,N-trimethylammonium chloride diallyldimethylammonium chloride and methylsulfate The anionic monomers are in their neutral form initially or are subsequently converted to their anionic form. These classes of compounds include polymerizable monomers which contain carboxy, sulfonate, and phosphate or phosphate groups. Such monomers are represented by:
.DTD:
acrylic acid methacrylic acid sodium acrylate and methacrylate vinylsulfonic acid sodium vinylsulfonate p-styrenesulfonic acid sodium p-styrenesulfonate 2- methacryloyloxyethylsulfonic acid 3-methacryloyloxy-2- hydroxypropylsulfonic acid 2-acrylamido-2-methylpropanesulfonic acid allylsulfonic acid 2-phosphatoethyl methacrylate Examples of cross-linking agents can be used in forming polymeric materials of this invention and include polyfunctional derivatives of acrylic acid, methacrylic acid, acrylamide, methacrylamide and multi- vinyl substituted benzenes, including but not limited to the following:
.DTD:
ethylene glycol diacrylate or dimethacrylate diethylene glycol diacrylate or dimethacrylate tetraethylene glycol diacrylate or dimethacrylate polyethylene glycol diacrylate or dimethacrylate polypropylene glycol diacrylate or methacrylate trimethylolpropane triacrylate or trimethacrylate Bisphenol A diacrylate or dimethacrylate ethoxylated Bisphenol A diacrylate or dimethacrylate pentaerythritol tri- and tetraacrylate or methacrylate tetramethylenediacrylate or dimethacrylate methylene bisacrylamide or methacrylamide dimethylene bisacrylamide or methacrylamide N,N'-dihydroxyethylene bisacrylamide or methacrylamide hexamethylene bisacrylamide or methacrylamide decamethylene bisacrylamide or methacrylamide divinyl benzene The copolymers described in this invention are prepared by radical polymerization through the incorporation of a free radical initiator. The initiator is chosen from those commonly utilized to polymerize vinyl type monomers and would include the following representative initiators:
.DTD:
2,2-azo-bis-isobutyronitrile 4,4'-azo-bis-(4-cyanopentanoic acid) t-butyl peroctoate benzoyl peroxide lauroyl peroxide methyl ethyl ketone peroxide diisopropyl peroxycarbonate The free radical initiator is normally used in amounts of from 0.01 to 2% by weight of the entire compound.
.DTD:
The materials of this invention can be polymerized directly in a suitable mold to form contact lenses directly. It is preferable to polymerize into sheet or rod stock from which contact lenses may be machined.
.DTD:
It is preferred to use the conventional approach when forming contact lenses such as used for polymethyl methacrylate (PMMA). In this approach, the formulations are polymerized directly into a 14 GB 2 117 387 A 14 sheet or rod from which blanks in the form of buttons, discs or other preformed shapes are cut. These blanks are then machined to obtain the lens surfaces. The resulting polymeric stock of blanks possesses the optical qualitites necessary to produce aberration-free oxygen- permeable, hard contact lenses in accordance with this invention. Oxygen permeability values of the contact lenses were generated by a procedure as described in ASTM D 1434 except that piano contact lenses are used instead of large flat 5 discs of material. The permeability apparatus was constructed in such a manner as to accept actual contact lenses and calibrated with other polymeric lenses of known permeability. As a comparison to the oxygen permeability data reported in the Examples, polymethyl methacrylate, polycarbonate, and polystyrene have oxygen permeabilities of 1,22, and 35 cm3mm/cm2sec cmHgx 10-1 , respectively.
.DTD:
The following examples are given to illustrate the invention and not meant to be limiting: 10 EXAMPLE 1 .DTD:
Synthesis of}-methacryloxypropyl-tris(3acetoxypropyldimethylsiloxy)silane A catalyst solution is prepared by adding, with stirring, 52 ml of concentrated sulfuric acid to a cooled mixture of 59 ml absolute ethanol and 66 ml of distilled water.
.DTD:
A 1000 ml round bottom flask, equipped with a magnetic stirring bar, is placed in a suitable size 15 container which will function as a water bath. To the flask is added 100 ml (0.42 moles) of Fmethacryloxypropyltrimethoxysilane and 300 ml (1.26 moles) of 3acetoxypropyldimethylacetoxy silane. The bath vessel is filled with water at a temperature of between 20 and 30 C. While stirring, 20 ml of catalyst solution (prepared earlier) is added dropwise from a dropping funnel into the flask. After the catalyst addition is complete, the reaction mixture is stirred at room temperature for 72 hours. 20 Approximately two volumes of distilled water are then added to the reaction mixture and the batch washed for several hours. The organic layer is then isolated and stripped of low boiling contaminants by vacuum distillation at a temperature of between 50 and 60 C. The monomer is then decolored with activated carbon yielding approximately 220 ml of T'-methacryloxy- propyltris(3acetoxypropylmethylsiloxy)silane. 25 EXAMPLE 2 .DTD:
Synthesis of F-methacryloxypropyl-bis(3-acetoxypropyldimethylsiloxy)(trimethylsiloxy)silane A catalyst solution is prepared by adding, with stirring, 52 ml of concentrated sulfuric acid to a cooled mixture of 59 ml absolute ethanol and 66 ml of distilled water.
.DTD:
A 1000 ml round bottom flask, equipped with a magnetic stirring bar, is placed in a suitable size container which will function as a water bath. To the flask is added 100 ml (0.42 moles) of T'methacryloxypropyltrimethoxysilane, 65 ml (0.42 moles) trimethylacetoxysilane and 200 ml (0.84 moles) 3-acetoxypropyldimethylacetoxysilane. The bath vessel is filled with water at a temperature of between 20 and 30 C. While stirring, 20 ml of catalyst solution (prepared earlier) is added dropwise from a dropping funnel intothe flask. After the catalyst addition is complete, the reaction mixture is stirred at room temperature for 72 hours. The upper oily layer is then isolated and stripped of low boiling contaminants by vacuum distillation at a temperature of between 50 and 60 C. The monomer is then decolored with activated carbon yielding approximately 200 ml of,-methacryloxypropyl-bis(3- ' acetoxypropyldimethylsiloxy) (trimethylsiloxy)silane.
.DTD:
EXAMPLE 3 40 .DTD:
Synthesis of]-methacryxyprpy(3-acetxyprpydimethysixy)bis(trimethysixy)siane A catalyst solution is prepared by adding, with stirring, 52 ml of concentrated sulfuric acid to a cooled mixture of 59 ml absolute ethanol and 66 ml of distilled water.
.DTD:
A 1000 ml round bottom flask, equipped with a magnetic stirring bar, is placed in a suitable size container which will function as a water bath. To the flask is added 100 ml (0.42 moles) of T'" 45 methacryloxypropyltrimethoxysilane, 130 ml (0.84 moles) trimethylacetoxysilane and 100 ml (0.42 moles) 3-acetoxypropyldimethylacetoxysilane. The bath vessel is filled with water at a temperature of between 20 and 30 C. While stirring, 20 ml of catalyst solution (prepared earlier) is added dropwise from a dropping funnel into the flask. After the catalyst addition is complete, the reaction mixture is stirred at room temperature for 72 hours. The upper oily layer is separated and washed with two 50 volumes of distilled water. The organic layer is then isolated and stripped of low boiling contaminants by vacuum distillation at a temperature of between 50 and 60 C. The monomer is then decolored with activated carbon yielding approximately 170 ml of F-methacryloxypropyl(3acetoxypropyldimethylsiloxy)-bis(trimethylsiloxy)silane.
.DTD:
EXAMPLE 4 .DTD:
Synthesis of F-methacryloxypropyl-bis(pentamethyldisiloxanyl) (3acetoxypropyldimethylsiloxy)silane 55 A catalyst solution is prepared by adding, with stirring, 52 ml of concentrated sulfuric acid to a cooled mixture of 59 ml absolute ethanol and 66 ml of distilled water.
.DTD:
A 1000 ml round bottom flask, equipped with a magnetic stirring bar, is placed in a suitable size container which will function as a water bath. To the flask is added 100 ml (0.42 moles) of T'methacryloxypropyltrimethoxysilane, 210 ml (0.84 moles) pentamethylacetoxydisiloxane and 100 ml 60 GB 2 117 387 A 15 (0,42 moles) 3-acetoxypropyldimethylacetoxysilane. The bath vessel is filled with water at a temperature of between 20 and 30 C. While stirring, 20 ml of catalyst solution (prepared earlier) is added dropwise from a dropping funnel into the flask. After the catalyst addition is complete, the reaction mixture is stirred at room temperature for 72 hours. The upper oily layer is separated and washed with two volumes of distilled water. The organic layer is then isolated and stripped of low 5 boiling contaminants by vacuum distillation at a temperature of between 50 and 60 C. The monomer is then decolored with activated carbon yielding approximately 230 ml of}methacryloxypropyl- bis(penta methy!disiloxanyl) (3-acetoxypropyldimethylsiloxy)silane.
.DTD:
EXAMPLE 5 .DTD:
Synthesis of 1,3-Bis(F-methacryloxypropyl)-l,l,3,3 tetra(3acetoxypropyldimethylsiloxy)disiloxane 10 A catalyst solution is prepared by adding, with stirring, 52 ml of concentrated sulfuric acid to a cooled mixture of 59 ml absolute ethanol and 66 ml of distilled water.
.DTD:
A 1000 ml round bottom flask, equipped with a magnetic stirring bar, is placed in a suitable size container which will function as a water bath. To the flask is added 100 ml (0.42 moles) of Vmethacn/Ioxypropyltri-methoxysi!lane and 200 ml (0.84 moles) of 3acetoxypropyldimethyl acetoxy 15 silane. The bath vessel is filled with water at a temperature of between 20 and 30 C. While stirring, 20 ml of catalyst solution (prepared earlier) is added dropwise from a dropping funnel into the flask. After the catalyst addition is complete, the reaction mixture is stirred at room temperature for 72 hours.
.DTD:
Approximately two volumes of distilled water are then added to the reaction mixture and the batch washed for several hours. The organic layer is then isolated and stripped of low boiling contaminants by 20 vacuum distillation at a temperature of between 50 and 60 C. The monomer is then decolored with activated carbon yielding approximately 100 ml of 1,3-Bis(-methacryloxy-propyl)-I,1,3,3 tetra(3acetoxypropyldimethylsiloxy)disiloxane.
.DTD:
EXAMPLE 6 .DTD:
Synthesis of 1-(},-methacryloxypropyl)-3-(3acetoxypropyl)tetra(trimethylsiloxy)disiloxane 25 A catalyst solution is prepared by adding, with stirring, 52 ml of concentrated sulfuric acid to a cooled mixture of 59 ml absolute ethanol and 66 ml of distilled water.
.DTD:
A 1000 ml round bottom flask, equipped with a magnetic stirring bar, is placed in a suitable size container which will function as a water bath. To the flask is added 100 ml (0.42 moles) of}methacryloxypropyltrimethoxysilane, 248 ml (1.68 moles) trimethylacetoxysilane and 96 ml (0.42 30 moles) 3-acetoxypropyltrimethoxysilane. The bath vessel is filled with water at a temperature of between and 30 C. While stirring, 40 ml of catalyst solution (prepared earlier) is added dropwise from a dropping funnel into the flask. After the catalyst addition is complete, the reaction mixture is stirred at room temperature for 72 hours. The upper oily layer is separated and washed with two volumes of distilled water. The organic layer is then isolated and stripped of low boiling contaminants by vacuum 35 distillation at a temperature of between 50 and 60 C. The monomer is then decolored with activated carbon yielding approximately 150 ml of 1-(,-methacryloxypropyl)-3-(3acetoxypropyl)tetra(trimethylsiloxy)disiloxane.
.DTD:
EXAMPLE 7 .DTD:
A mixture of 20 parts of the substituted polysiloxane monomer of Example 1 (A3TRIS), 80 parts o 40 methylmethacrylate (MMA) and 0.4 parts of o,o'-azobisisobutyronitrile (AIBN) is placed in test tubes which are purged with nitrogen then sealed with a serum cap. The test tubes are placed in a water bath at 40 C and allowed to polymerize for 3 days. The tubes are then placed in a 65 C oven for an additional time period of 3 days, after which the polymerized rods are removed from the tubes. The hard, transparent rods are then subjected to conditioning for approximately 24 hours at 100 C under 45 vacuum to complete the polymerization process and relieve any mechanical stresses present. The conditioned rods are then machined to contact lens blanks (a disk 1/2 inch in diameter by 3/16 inch thick). The Rockwell Hardness of this material is 119 on the R scale (ASTM D-785).
.DTD:
A contact angle measurement obtained by placing a drop of water on the polished flat surface indicates a contact angle of 59 degrees. 50 The oxygen permeability of a 0.20 mm thick contact lens is 25 cm3 mm/cm2sec cm Hg x 10-1 when measured by the method described in the specification.
.DTD:
EXAMPLE 8 .DTD:
A mixture of 40 parts of the substituted polysiloxane monomer of Example 1 (A3TRIS), 60 parts of methylmethacrylate (MMA) 2 parts of tetraethylene glycol dimethacrylate (TGD) and 0.4 parts of ,o'azobisisobutyronitrile (AIBN) is placed in test tubes which are purged with nitrogen then sealed with serum caps. The test tubes are placed in a water bath at 40 C and allowed to polymerize for 3 days. The tubes are then placed in a 65 C oven for an additional time period of 3 days, after which the polymerized rods are removed from the tubes. The hard transparent rods are then subjected to conditioning for approximately 24 hours at 100 C under vacuum to complete the polymerization 60 process and relieve any mechanical stresses present. The conditioned rods are then machined to 16 GB 2 117 387 A 16 contact lens blanks (a disk 1/2 inch in diameter by 3/16 inch thick). The Rockwell Hardness of this material is 119 on the R scale (ASTM D-785).
.DTD:
A contact angle measurement obtained by placing a drop of water on the polished flat surface indicates a contact angle of 58 degrees.
.DTD:
The oxygen permeability of a 0.20 mm thick contact lens is 56 cm3 mm/cm2sec cm Hg x 10-l when measured by the method described in the specification.
.DTD:
EXAMPLE 9 .DTD:
Utilizing the experimental procedure of Example 7 this Example illustrates the preparation and properties of copolymer containing varying proportions of the substituted polysiloxane monomer of Example 3 (AITRIS) and methylmethacrylate (MMA).
.DTD:
Compositon (wt.%) Properties MMA AITRIS AIBN 39.9 59.9 0.2 T, H, R 29.9 69.9 0.2 1", SR 19.9 79.9 0.2 T, S 0 99.8 0.2 T, E T = Transparent H = Hard R = Rigid S = Soft E = Elastomeric EXAMPLE 10 .DTD:
Utilizing the experimental procedures of Example 7, this Example illustrates the preparation and properties of hard contact lenses in which the level of substituted polysiloxane monomer (ALTRIS) is changed.
.DTD:
Composition (wt.%) Hardness Oxygen MMA AITRIS MA TGD AIBN Rockwell R Permeability 56.5 37.7 4.7 0.9 0.2 112 46 51.8 42.4 4.7 0.9 0.2 107 67 47.1 47.1 4.7 0.9 0.2 1 O0 108 Methacrylic acid Tetraethyleneglycol dimethacrylate Value in cm3 mm/cm2 sec cm Hg x 10l EXAMPLE 11 .DTD:
Utilizing the experimental procedures of Example 7, this Example illustrates the preparation and properties of materials suitable for semirigid contact lenses.
.DTD:
Composition (wt.%) MMA A2TRIS MA TEDGM A IBN PROPERTIES 49.4 49.4 0.0 1.0 0.2 T, SR 40 47.1 47.1 4.7 0.9 0.2 T, SR T = Transparent SR = Semi-rigid 17 GB 2 117 387 A 17 EXAMPLE 12 .DTD:
A mixture of 24.7 parts of the polysiloxane monomer of Example 3 (AITRIS), 74.1 parts of methoxyethylacrylate (MEA), 1.0 parts of tetraethylene glycol dimethacrylate (TGD) and 0.2 parts of ,ol,-azobisisobutyronitrile (AIBN) is polymerized in a test tube, under nitrogen in a stepwise fashion. The polymerization schedule was 3 days at 40 C, 3 days at 65 C then 1 day at 100 C under vacuum. The resultant plug is transparent, flexible and suitable as a soft contact lens material.
.DTD:
EXAMPLE 13 .DTD:
A mixture of 49.4 parts of the polysiloxane monomer of Example 3 (AITRIS), 49.4 parts of methoxyethylacrylate (MEA), 1.0 parts of tetraethylene glycol dimethacrytate (TGD), and 0.2 parts of ,ó,-azobisisobutyronitrile (AIBN) is polymerized in a test tube, under nitrogen in a stepwise fashion. The polymerization schedule was 3 days at 40 C, 3 days at 65 C then 1 day at 100 C under vacuum. The resultant plug is transparent, flexible and suitable as a soft contact lens material.
.DTD:
EXAMPLE 14 .DTD:
A mixture of 24.7 parts of the polysiloxane monomer of Example 3 (AITRIS), 74.1 parts of butoxyethylmethacrylate (BEM), 1.0 parts of tetraethylene glycol dimethacrylate (TGD) and 0.2 parts of 15 ,oi-azobisisobutyronitrile (AIBN) is polymerized in a test tube, under nitrogen, in a stepwise fashion. The polymerization schedule was 3 days at 40 C, 3 days at 65 C then 1 day at 100 C under vacuum. The resultant plug is transparent, flexible and suitable as a soft contact lens material.
.DTD:
EXAMPLE 15 .DTD:
A mixture of 49.4 parts of the polysiloxane monomer of Example 3 (AITRIS), 49.4 parts of 20 butoxyethylmethacrylate (BEM), 1.0 parts of tetraethylene glycol dimethacrylate (TGD) and 0.2 parts of ,ó-azobis-isobut/ronitrile (AIBN) is polymerized in a test tube, under nitrogen, in a stepwise fashion.
.DTD:
The polymerization schedule was 3 days at 40 C, 3 days at 65 C then 1 day at 100 C under vacuum.
.DTD:
The resultant plug is transparent, flexible and suitable as a soft contact lens material.
.DTD:
EXAMPLE 16.. 25 A mixture of 49.4 parts of the polysiloxane monomer of Example 1 (A3TRIS), 49.4 parts of butoxyethylmethacrylate (BEM), 1.0 parts of tetraethylene glycol dimethacrylate (TGD) and 0.2 parts of oi,ó-azobis-isobutyronitrile (AIBN) is polymerized in a test tube, under nitrogen, in a stepwise fashion.
.DTD:
The polymerization schedule was 3 days at 40 C, 3 days at 65 C then 1 day at 100 C under vacuum.
.DTD:
The resultant plug is transparent, flexible and suitable as a soft contact lens material. 30 : -..:
.DTD:
EXAMPLE 17..
.DTD:
A mixture of 74.1 parts of the polysiloxane monomer of Example 1 (A3TRIS), 24.7 parts of butoxyethylmethacrylate (BEM), 1.0 parts of tetraethylene glycol dimethacrylate (TGD) and 0.2 parts of ol,ó-azobis-isobutyronitile (AIBN) is polymerized in a test tube, Under nitrogen, in a stepwise fashion.
.DTD:
The polymerization schedule was 3 days at 40 C, 3 days at 65 C then 1 day at 100 C under vacuum. 35 The resultant plug is transparent, flexible and suitable as a soft contact lens material.
.DTD:
EXAMP LE 18 Utilizing the experimental procedures of Example 7this Example illustrates the preparation and properties of copolymers containing various proportions of the substituted monomer of Example 4 (P2ATRIS), methylmethacrylate (MMA), methacrylic acid (MA) and tetraethyleneglycol-dimethacrylate 40 (TGD).:
.DTD:
Composition (Wt.%) HARDNESS MMA P2ATRIS MA TGD AIBN ROCKWELL R 63.9 35.0 -- 0.9 0.2 116 53.9 45.0 m 0.9 0.2 108 48.9 50.0 -- 0.9 0.2 96 53.0 43.5 2.4 0.9 0.2 110 50.7 43.5 4.7 0.9 0.2 113 18 GB 2 117 387 A 18 EXAMPLE 19 .DTD:
Utilizing the experimental procedures of Example 7 this Example illustrates the preparation and properties of copolymer containing varying proportions of the substituted monomer of Example 5 (A4D and Methylmethacrylate (MMA).
.DTD:
Composition (wt.%) MMA A4D AIBN Properties 59.8 40.0 0.2 T, H 49.8 50.0 0.2 T, H 39.8 60.0 0.2 T, H 29.8 70.0 0.2 T, H T = Transparent H = Hard EXAMPLE 20 .DTD:
A mixture of 50 parts of the polysiloxane monomer of Example 6, 45 parts of methylmethacrylate, parts of methacrylic acid and 0.2 parts of o,o1-azobisisobutyronitrile was polymerized according to the procedures set forth in Example 7. The resultant polymer was hard and transparent and suitable as a hard contact lens material. The Rockwell R Hardness of the material was 113 and the oxygen 10 permeability was found to be 150. Contact lenses machined from this material were found to be dimensionally stable and wettable by human tears.
.DTD:
The following Table illustrates the general combinations of materials as preferred for use in the present invention to form polymerized organosiloxane materials in a form suitable for machining or casting as contact lenses: 15 Oxygen Permeable Siloxane Material Formulation 1 Formulation 2 Formulation 3 Oxygen permeable siloxane material of this invention 100% 25--98% 25--98% Hardening Agent 0 75--2% 75--1% Hydrophilic Agent 0 0 1%--10% The polysiloxanes of this invention can be used in place of the siloxane materials of prior art lens polymeric combinations. For example, the siloxanes of this invention can be used instead of the siloxanyl alkyl esters in the contact lens formulations of U.S. Patent 4,152,508 issued May 1, 1979.
.DTD:
The above Examples are merely illustrative of the present invention. Many combinations are 20 possible. Both hard, semi-hard, and soft contact lenses can be advantageously produced using the compositions of this invention.
.DTD:
Usual additives such as tints, colorants, antioxidants, stabilizers, absorbers and the like can be incorporated in the formulations of this invention if desired. All lenses can have conventional hardening agents, softening agents, wetting agents, hydrophilic hardening agents and the like incorporated therein 25 so long as desired contact lens properties are retained. Both hard and soft lenses can be made depending on the additives, if any, used with the polysiloxanes of this invention.
.DTD:
.CLME:

Claims (1)

  1. CLAIMS .CLME:
    1. A contact lens material formed of a siloxane containing one or more unsaturated polymerizable groups having the following formula:
    .CLME:
    19 GB 2 117 387 A 19 I ! o | X-'-Si-o i I O O I %- - $c.- R-g I SL-R-X O I N - - S. -X R /, wherein:
    .CLME:
    X is selected from the group consisting essentially of unsaturated polymerizable methacrylate, acrylate, hydrogen or "'Z" groups and mixtures thereof, R is selected from the group consisting essentially of alkylene, cycloalkylene groups having from 1 to about 10 carbon atoms, arylene groups and mixtures thereof, a is an integer from 0 to about 10 where each "a" may be the same or different.
    .CLME:
    n is an integer from 0 to about 10, Z groups are selected from the group consisting essentially of acetoxy, carbomethoxy, glycidoxy, glyceryl, and carboxy with at least one "X" being a "Z" group.
    .CLME:
    2. A contact lens material in accordance with claim 1 wherein said siloxane is 1,3-bis(},- m ethacryloxypropyl- 1,1,3,3-tetra(3acetoxypropyldimethylsiloxy)disiloxane.
    .CLME:
    3. A contact lens material in accordance with claim 1 wherein said siloxane is p methacryloxypropyl-tris(4acetoxyphenyldimethylsiloxy)silane.
    .CLME:
    4. A contact lens material in accordance with claim 1, wherein said siloxane is,methacryloxypropyl-tris(2-carboxyethyldimethylsiloxy)silane.
    .CLME:
    5. A contact lens material in accordance with claim 1, wherein said siloxane is},methacryloxypropyl-tris(2-acetoxyethyldimethylsiloxy)silane, 6. A contact lens material in accordance with claim 1 wherein said siloxane is 1 -úmethacryloxymethyl-3-(3-acetoxypropyl)- 1,1,3,3-tetra methyldisiloxane.
    .CLME:
    7. A contact lens material in accordance with claim 1 wherein said siloxane is methacryloxypropyl-bis(trimethylsiloxy)-(3acetoxypropyldimethylsiloxy)silane.
    .CLME:
    8. A contact lens material in accordance with claim 1 wherein said siloxane is}methacryxyprpy-bis(trimethysixy)-(3carbmethxyprpydimethysixy)siane 9. A contact lens material in accordance with claim 1 wherein said siloxane is},methacryloxypropyl-bis(trimethylsiloxy)-(3hydroxypropyidimethylsiloxy)silane.
    .CLME:
    10. A contact lens material in accordance with claim 1 wherein said siloxane is methacryloxypropyl-bis(trimethylsiloxy)-(3carboxypropyldimethylsiloxy)silane.
    .CLME:
    11. A contact lens material in accordance with claim 1 wherein said siloxane is methacryloxypropyl-bis(3-acetoxypropyldimethylsiloxy)(trimethylsiloxy)silane.
    .CLME:
    12. A contact lens material in accordance with claim 1 wherein said siloxane is,methacryloxypropyl-bis(3-ca rbomethoxypropyldimethylsiloxy) (trimethylsiloxy)silane.
    .CLME:
    13. A contact lens material in accordance with claim 1 wherein said siloxane is},o methacryloxypropyl-bis(3-hydroxypropyldimethylsiloxy)(trimethylsiloxy)silane.
    .CLME:
    14. A contact lens material in accordance with claim 1 wherein said siloxane is methacryloxypropyl-bis(3-carboxypropyldimethylsiloxy)(trimethylsiloxy)silane.
    .CLME:
    15. A contact lens material in accordance with claim 1 wherein said siloxane is 9methacryloxypropyl-tris(3-acetoxypropyldimethylsiloxy)silane.
    .CLME:
    GB 2 117 387 A 20 16. A contact lens material in accordance with claim 1 wherein said siloxane ts},methacryloxypropyl-tris(3carbomethoxypropyldimethylsiloxy)silane.
    .CLME:
    17. A contact lens material in accordance with claim 1 wherein said siloxane 0s Fmethacryloxypropyl-tris(3-hydroxypropyldimethylsiloxy)silane.
    .CLME:
    18. A contact lens material in accordance with claim 1 wherein said siloxane is Fmethacryxyprpy-bs(pentamethydisixany)-(3acetxyprpydimethysixy)siane 19. A contact lens material in accordance with claim 1 whereto said siloxane is Fmethacryxyprpy-bis(pentamethydisixany)-(3carbmethxyprpydimethysixy)siane 20. A contact lens material in accordance with claim 1 wherein said siloxane is Fmethacryxyprpy-bis(pentamethydisioxany)-(3- hydrxyprpydimethysixy)siane 21, A contact lens material m accordance with claim 1 wherein said siloxane is]Jmethacryxyprpy-bis(pentamethydisixany)-(3carbxyprpydimethysixy)siane 22. A contact lens material m accordance with claim 1 wherein said siloxane =s T'methacryloxypropyl)-3-(3-acetoxypropyl) - tetratrimethylsiloxy)disiloxane.
    .CLME:
    23. A contact lens material m accordance with claim 1 wherein said siloxane is 1-(]methacryloxypropyl)-3-(3-carbomethoxypropyl)tetratrimethylsiloxy)disiloxane.
    .CLME:
    24. A contact lens material m accordance with claim 1 wherein siloxane is 1-(Fmethacryloxypropyl)-3-(3-hydroxypropyl)tetra(trimethylsiloxy)disiloxane.
    .CLME:
    25. A contact lens material m accordance with claim 1 wherein said siloxane is 1-(úmethacryloxypropyl)-3-(3-carboxypropyl)tetra(trimethylsiloxy)disiloxane.
    .CLME:
    26. A contact lens formed of a siloxane containing one or more unsaturated polymerizable groups having the following formula:
    .CLME:
    I- R I O I - R - Jt-R-X f X i I - E - SL-R-X l 0 S--- O- ' 0 I <- R - SLR-; I y, O " "" " S--x 0 t N- - So- R-X R X wherein:
    .CLME:
    X is selected from the group consisting essentially of unsaturated polymerizable methacrylate, 25 acrylate, hydrogen or "Z'" groups and mixtures claim 26 continued:
    .CLME:
    thereof, R is selected from the group consisting essentially of alkylene, cycloalkylene groups having from 1 to about 10 carbon atoms, arylene groups and mixtures thereof.
    .CLME:
    a is an integer from 0 to about 10 where each "a" may be the same or different, 30 n is an integer from 0 to about 10, Z groups are selected from the group consisting essentially of acetoxy, carbomethoxy, glycidoxy, glyceryl, and carboxy with at least one "X" being a "Z" group.
    .CLME:
    27. A contact lens material in accordance with claim 26 wherein said siloxane is copolymerized with a hardening agent. 35 28. A contact lens in accordance with claim 26 wherein said siloxane is copolymerized with a wetting agent.
    .CLME:
    21 GB 2 117 387 A 21 29. A contact lens in accordance with claim 28 and further including a hardening agent.
    .CLME:
    30. A contact lens in accordance with claim 29 wherein said hardening agent is selected from the group consisting of acrylic, methacrylic and itaconic acid derivatives including esters of a C1---C2o monohydric or polyhydric alkarol, phenol and an acid selected from the class consisting essentially of acrylic and methacrylic acid, itaconate mono and diester. 5 31. A contact lens in accordance with claim 30 wherein said wetting agent is selected from the group consisting of neutral monomers, hydrophilic cationic monomers and hydrophilic anionic monomers.
    .CLME:
    32. A contact lens material according to claim 1, substantially as hereinbefore described and exemplified. 10 33. A contact lens according to claim 26, substantially as hereinbefore described and exemplified.
    .CLME:
    Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1983. Published by the Patent Office, Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
    .CLME:
GB08304358A 1982-03-29 1983-02-17 Silicone-containing contact lens material and contact lenses made thereof Expired GB2117387B (en)

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US4508884A (en) * 1983-05-25 1985-04-02 Coopervision, Inc. Oxygen permeable hard contact lens

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US4647282A (en) * 1985-08-27 1987-03-03 Moskovsky Nauchno-Issledovatelsky Institut Mikrokhirurgii Glaza Material for ocular prosthetics
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US4780488A (en) * 1986-08-29 1988-10-25 Ciba-Geigy Corporation Wettable, flexible, oxygen permeable, substantially non-swellable contact lens containing polyoxyalkylene backbone units, and use thereof
US4861840A (en) * 1986-12-03 1989-08-29 Barnes-Hind, Inc. Novel siloxanyl acrylic monomer and gas-permeable contact lenses made therefrom
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US5149592A (en) * 1990-05-09 1992-09-22 Avery Dennison Corporation Ultraviolet radiation curable clearcoat
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US4463149A (en) 1984-07-31
AU1185283A (en) 1983-10-06
FR2523981B1 (en) 1987-02-06
CA1196748A (en) 1985-11-12
GB2117387B (en) 1985-08-14
GB8304358D0 (en) 1983-03-23
AU560515B2 (en) 1987-04-09
DE3309631A1 (en) 1983-10-06
JPS58169127A (en) 1983-10-05

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